Method of forming a scintillation crystal and a radiation detection apparatus including a scintillation crystal including a rare earth halide

ABSTRACT

A scintillation crystal can include Ln(1-y)REyX3, wherein Ln represents a rare earth element, RE represents a different rare earth element, y has a value in a range of 0 to 1, and X represents a halogen. In an embodiment, the scintillation crystal is doped with a Group 1 element, a Group 2 element, or a mixture thereof, and the scintillation crystal is formed from a melt having a concentration of such elements or mixture thereof of at least approximately 0.02 wt. %. In another embodiment, the scintillation crystal can have unexpectedly improved proportionality and unexpectedly improved energy resolution properties. In a further embodiment, a radiation detection apparatus can include the scintillation crystal, a photosensor, and an electronics device. Such a radiation detection apparatus can be useful in a variety of applications.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of and claims priority under 35U.S.C. § 120 to U.S. patent application Ser. No. 14/064,981 entitled“Radiation Detection Apparatus Including A Scintillation CrystalIncluding a Rare Earth Halide,” by Dorenbos et al, filed Oct. 28, 2013,which is a non-provisional application that claims priority under 35U.S.C. § 119(e) to U.S. Provisional Patent Application No. 61/719,405entitled “Scintillation Crystal Including a Rare Earth Halide, and aRadiation Detection Apparatus Including the Scintillation Crystal,” byDorenbos et al., filed Oct. 28, 2012, both of which are incorporatedherein by reference in their entireties.

FIELD OF THE DISCLOSURE

The present disclosure is directed to scintillation crystals includingrare earth halides and radiation detection apparatuses including suchscintillation crystals.

BACKGROUND

Radiation detection apparatuses are used in a variety of applications.For example, scintillators can be used for medical imaging and for welllogging in the oil and gas industry as well for the environmentmonitoring, security applications, and for nuclear physics analysis andapplications. Scintillation crystals used for radiation detectionapparatuses can include rare earth halides. Further improvement ofscintillation crystals is desired.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated by way of example and are not limited in theaccompanying figures.

FIG. 1 includes an illustration of a radiation detection apparatus inaccordance with an embodiment.

FIG. 2 includes a plot of energy resolution as a function of energy fordifferent compositions of LaBr₃:Ce scintillation crystals at gamma rayenergies in a range of approximately 8 keV to approximately 90 keV.

FIG. 3 includes a plot of energy resolution ratio as a function ofenergy for different compositions of LaBr₃:Ce scintillation crystals atgamma ray energies in a range of approximately 276 keV to approximately662 keV.

FIG. 4 includes a plot of energy resolution as a function of energy fordifferent compositions of CeBr₃ scintillation crystals at gamma rayenergies in a range of approximately 8 keV to approximately 90 keV.

FIG. 5 includes a plot of energy resolution ratio as a function ofenergy for different compositions of CeBr₃ scintillation crystals atgamma ray energies in a range of approximately 276 keV to approximately662 keV.

FIG. 6 includes a plot of non-proportionality for different compositionsof LaBr₃:Ce scintillation crystals at gamma ray energies in a range ofapproximately 8 keV to approximately 1332 keV.

FIG. 7 includes a plot of non-proportionality for different compositionsof LaBr₃:Ce scintillation crystals at gamma ray energies in a range ofapproximately 9 keV to approximately 100 keV.

FIG. 8 includes a plot of non-proportionality for different compositionsof CeBr₃ scintillation crystals at gamma ray energies in a range ofapproximately 8 keV to approximately 1332 keV.

FIG. 9 includes a plot of non-proportionality for different compositionsof CeBr₃ scintillation crystals at gamma ray energies in a range ofapproximately 11 keV to approximately 100 keV.

FIG. 10 includes a plot of relative light output for differentcompositions of LaBr₃ scintillation crystals over a range oftemperatures.

Skilled artisans appreciate that elements in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the elements in the figures maybe exaggerated relative to other elements to help to improveunderstanding of embodiments of the invention.

DETAILED DESCRIPTION

The following description in combination with the figures is provided toassist in understanding the teachings disclosed herein. The followingdiscussion will focus on specific implementations and embodiments of theteachings. This focus is provided to assist in describing the teachingsand should not be interpreted as a limitation on the scope orapplicability of the teachings.

The term “averaged,” when referring to a value, is intended to mean anaverage, a geometric mean, or a median value.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of features is notnecessarily limited only to those features but may include otherfeatures not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive-or and not to an exclusive-or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The use of “a” or “an” is employed to describe elements and componentsdescribed herein. This is done merely for convenience and to give ageneral sense of the scope of the invention. This description should beread to include one or at least one and the singular also includes theplural, or vice versa, unless it is clear that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. The materials, methods, andexamples are illustrative only and not intended to be limiting. To theextent not described herein, many details regarding specific materialsand processing acts are conventional and may be found in textbooks andother sources within the scintillation and radiation detection arts.

FIG. 1 illustrates an embodiment of a radiation detection apparatussystem 100. The radiation detection apparatus system can be a medicalimaging apparatus, a well logging apparatus, a security inspectionapparatus, nuclear physics applications, or the like. In a particularembodiment, the radiation detection apparatus can be used for gamma rayanalysis, such as a Single Positron Emission Computer Tomography (SPECT)or Positron Emission Tomography (PET) analysis.

In the embodiment illustrated, the radiation detection apparatus 100includes a photosensor 101, an optical interface 103, and ascintillation device 105. Although the photosensor 101, the opticalinterface 103, and the scintillation device 105 are illustrated separatefrom each other, skilled artisans will appreciate that photosensor 101and the scintillation device 105 can be coupled to the optical interface103, with the optical interface 103 disposed between the photosensor 101and the scintillation device 105. The scintillation device 105 and thephotosensor 101 can be optically coupled to the optical interface 103with other known coupling methods, such as the use of an optical gel orbonding agent, or directly through molecular adhesion of opticallycoupled elements.

The photosensor 101 may be a photomultiplier tube (PMT), asemiconductor-based photomultiplier, or a hybrid photosensor. Thephotosensor 101 can receive photons emitted by the scintillation device105, via an input window 116, and produce electrical pulses based onnumbers of photons that it receives. The photosensor 101 is electricallycoupled to an electronics module 130. The electrical pulses can beshaped, digitized, analyzed, or any combination thereof by theelectronics module 130 to provide a count of the photons received at thephotosensor 101 or other information. The electronics module 130 caninclude an amplifier, a pre-amplifier, a discriminator, ananalog-to-digital signal converter, a photon counter, another electroniccomponent, or any combination thereof. The photosensor 101 can be housedwithin a tube or housing made of a material capable of protecting thephotosensor 101, the electronics module 130, or a combination thereof,such as a metal, metal alloy, other material, or any combinationthereof.

The scintillation device 105 includes a scintillation crystal 107. Thecomposition of the scintillation crystal 107 will be described in moredetail later in this specification. The scintillation crystal 107 issubstantially surrounded by a reflector 109. In one embodiment, thereflector 109 can include polytetrafluoroethylene (PTFE), anothermaterial adapted to reflect light emitted by the scintillation crystal107, or a combination thereof. In an illustrative embodiment, thereflector 109 can be substantially surrounded by a shock absorbingmember 111. The scintillation crystal 107, the reflector 109, and theshock absorbing member 111 can be housed within a casing 113.

The scintillation device 105 includes at least one stabilizationmechanism adapted to reduce relative movement between the scintillationcrystal 107 and other elements of the radiation detection apparatus 100,such as the optical interface 103, the casing 113, the shock absorbingmember 111, the reflector 109, or any combination thereof. Thestabilization mechanism may include a spring 119, an elastomer, anothersuitable stabilization mechanism, or a combination thereof. Thestabilization mechanism can be adapted to apply lateral forces,horizontal forces, or a combination thereof, to the scintillationcrystal 107 to stabilize its position relative to one or more otherelements of the radiation detection apparatus 100.

As illustrated, the optical interface 103 is adapted to be coupledbetween the photosensor 101 and the scintillation device 105. Theoptical interface 103 is also adapted to facilitate optical couplingbetween the photosensor 101 and the scintillation device 105. Theoptical interface 103 can include a polymer, such as a silicone rubber,that is polarized to align the reflective indices of the scintillationcrystal 107 and the input window 116. In other embodiments, the opticalinterface 103 can include gels or colloids that include polymers andadditional elements.

The scintillation crystal 107 can include a rare earth halide. As usedherein, rare earth elements include Y, Sc, and the Lanthanide serieselements. In an embodiment, the scintillation crystal 107 can includeone or more other rare earth elements. Thus, the scintillation crystal107 can have chemical formula as set forth below.Ln_((1-y))RE_(y)X₃, wherein:

Ln represents a rare earth element;

RE represents a different rare earth element;

y has a value in a range of 0 to 1 formula unit (“f.u.”); and

X represents a halogen.

In particular embodiment, Ln can include La, Gd, Lu, or any mixturethereof; and RE can include Ce, Eu, Pr, Tb, Nd, or any mixture thereof.In a particular embodiment, the scintillation crystal 107 can beLa_((1-y))Ce_(y)Br₃. In particular embodiments, LaBr₃ and CeBr₃ arewithin the scope of compositions described.

In another a further embodiment y can be 0 f.u., at least approximately0.0001 f.u., at least 0.001 f.u., or at least approximately 0.05 f.u. Ina further embodiment, y may be 1 f.u., no greater than approximately 0.2f.u., no greater than approximately 0.1 f.u., no greater thanapproximately 0.05 f.u, or no greater than approximately 0.01 f.u. In aparticular embodiment, y is in a range of approximately 0.01 f.u. toapproximately 0.1 f.u. In a further embodiment, y is no greater thanapproximately 0.99 f.u., no greater than approximately 0.9 f.u., or nogreater than approximately 0.8 f.u. X can include a single halogen orany mixture of halogens. For example, X can include Br, I, or anymixture thereof.

The rare earth halide can further include a co-dopant or a dopantincluding a Group 1, a Group 2 element, or any mixture thereof. Group 1elements can include Li, Na, Rb, Cs, or any mixture thereon. In aparticular embodiment, the Group 1 element is Na. Group 2 elements caninclude Mg, Ca, Sr, Ba, or any mixture thereon. In a particularembodiment, the Group 2 element is Ca or Sr. A crystal that includesLaBr₃ co-doped with Ce and Sr has a peak emission that is at a longerwavelength as compared to a crystal that includes LaBr₃ doped with Ce.Further, when La_((1-y))Ce_(y)Br₃ is doped with Sr, the light output canbe more constant than La_((1-y)) Ce_(y)Br₃ over the range of −40° C. to175° C., and is brighter than La_((1-y))Ce_(y)Br₃ at temperatures higherthan 50° C. Thus, La_((1-y))Ce_(y)Br₃ is doped with Sr may be useful forapplications that involve extreme temperature excursions, such as oilwell logging and space applications. Similar to La_((1-y))Ce_(y)Br₃,CeBr₃ doped with Sr is brighter than CeBr₃ at temperatures higher than50° C. When La_((1-y))Ce_(y)Br₃ is doped with Ba, the light output maybe higher than the light output of La_((1-y))Ce_(y)Br₃ over the range ofroom temperature (approximately 22° C.) to about 70° C.La_((1-y))Ce_(y)Br₃ is doped with Ba may be useful for outdoorapplications, for example for port-of-entry detectors that can be usedfor vehicles and cargo.

In a further embodiment, the co-dopant or dopant can include at leasttwo different Group 1 elements, at least two different Group 2 elements,or at least one Group 1 element and at least one Group 2 element. In anembodiment, the content of the co-dopant or dopant can be measured asthe amount of co-dopant or dopant in a melt used to form the rare earthhalide. The co-dopant or dopant concentration in the melt can be atleast approximately 0.02 wt. %, or in particular at least approximately0.08 wt. %, at least approximately 0.2 wt. %, or more particularly atleast approximately 0.3 wt. %, or even more particularly 0.4 wt. %. Inanother embodiment, the co-dopant or dopant concentration in the meltmay be no greater than approximately 1.0 wt. %, or in particular nogreater than approximately 0.9 wt. %, or more particularly no greaterthan approximately 0.7 wt. %. In a particular embodiment, the co-dopantor dopant concentration in the melt can be in a range approximately 0.2wt. % to approximately 0.9 wt. % or more particularly, in a range ofapproximately 0.3 wt. % to 0.7 wt. %.

The starting materials can include metal halides of the same halogen ordifferent halogens. For example, a rare earth bromide and SrBr₂ or NaBrcan be used. In another embodiment, some of the bromide-containingcompounds may be replaced with iodide-containing compounds. Thescintillation crystal can be formed using a conventional technique froma melt. The method can include the Bridgman method, Czochralski crystalgrowth method, or Kyropolis growth method.

Scintillation crystals that include a Group 1 element-doped or a Group 2element-doped rare earth halide having concentrations as previouslydescribed provide good scintillating properties, including energyresolution at energies in a range of 10 keV to 2000 keV. In anotherembodiment, co-doped or doped rare earth halides can provide unexpectedresults as compared to other rare earth halide scintillation crystals,particularly at low energies. In a particular embodiment, the lowerenergies can be in a range of approximately 10 keV to approximately 60keV. More particularly, the Group 2 element-doped scintillation crystalshave unusually good proportionality at lower energies, and the Group 1element-doped and Group 2 element-doped scintillation crystals have goodenergy resolution over a wide range of energies. The range of 10 keV to356 keV can be further divided into ranges of approximately 10 keV to 30keV, 30 keV to 60 keV, 60 keV to 356 keV. The range of 356 keV to 1332keV is also examined. While improved performance occurs within each ofthe ranges, the relative improvement may be more significant for therange of 10 to 60 keV, as compared to the range of 356 keV to 1332 keVor even higher energies. The better performance at lower energies isparticularly significant for medical imaging applications. Thescintillation crystals can be used in other applications, such as welllogging in the oil and gas industry as well for the environmentmonitoring, security applications, and for nuclear physics analysis andapplications.

Energy resolution is the energy range at full-width of half maximum(“FWHM”) divided by the energy corresponding to the peak, expressed as apercent. A lower number for energy resolution means that the peak can beresolved more readily. Values for energy resolution may depend on themetrology equipment and the measurement techniques.

In an embodiment, measurements for energy resolution may be performed onscintillation crystals that varied in size from approximately 0.01 cm³to approximately 0.2 cm³. The crystals can be wrapped with a reflectoron the sides and one end. Alternatively, the crystals may be placed on awindow of a PMT and covered with the reflector. In a particularembodiment, the reflector may be a specular reflector or a diffusereflector. For example, the reflector may include an aluminum foil,aluminized polyester (e.g. aluminized Mylar™-brand polyester), or apolytetrafluoroethylene (“PTFE”) sheet reflector. The scintillationcrystal can be placed in a housing where scintillating light passesthrough a sapphire or quartz window.

The housed scintillation crystal can be interfaced to a PMT. In anembodiment, the PMT can be a non-saturated photomultiplier. Bynon-saturated, the photomultiplier operates in a mode in whichsignificantly more electrons may be generated with a significantlyhigher rate of photons striking the photocathode of the photomultiplier.An exemplary PMT can be a Hamamatsu Model R1791 PMT (available fromHamamatsu Photonics Deutschland GmbH of Herrsching am Ammersee, Del.)run at 400 V. One or more desired isotopes that emit radiation can beplaced one at a time at a predetermined distance, for example,approximately 150 mm (6 inches), from the sample. The energy spectra ofeach isotope and each crystal can be obtained from an ORTEC Model 672spectroscopic amplifier (available from AMETEK GmbH of Meerbusch, Del.)with a 10 μs shaping time.

In another embodiment, different equipment may be used. For example, aPMT can be Model 9305 from ET Enterprises Ltd. of Uxbridge, U.K., run at900 V. The energy spectra of each isotope and each crystal can beobtained from a multi-channel analyzer that performs bi-polar shaping ata 0.25 micro-s shaping time. An exemplary multichannel analyzer can beobtained from Canberra Industries Inc. of Meriden Conn., model Aptec55008 that has bi-polar shaping, 0.25 micro-s shaping time, and 11-bitdigitization. After reading this specification, skilled artisans will beable to select metrology equipment for their particular applications.

After reading this specification, skilled artisans will appreciate thatthe energy resolution values that they obtain may change if themetrology equipment and the measurement techniques are changed. Theenergy resolution values described below can be obtained using thepreviously described metrology equipment and the measurement conditionsto provide a more accurate comparison of energy resolution valuesbetween different samples.

Energy resolution ratio (“ER Ratio”) may be used to compare the energyresolutions of different compositions of materials for a particularenergy or range of energies. ER Ratio can allow for a better comparisonas opposed to energy resolution because ER Ratios can be obtained usingsubstantially the same metrology equipment and techniques. Thus,variations based on metrology equipment and techniques can besubstantially eliminated.

In an embodiment, the ER Ratio is the energy resolution of a particularcrystal at a particular energy or range of energies divided by theenergy resolution of another crystal at substantially the same energy orrange of energies, wherein the energy spectra for the crystals areobtained using the same or substantially identical metrology equipmentand techniques. In an embodiment, LaBr₃:Ce crystals having a co-dopantmay be compared to LaBr₃:Ce crystals without a co-dopant. In anotherembodiment, a doped CeBr₃ crystal can be compared to a substantiallyundoped CeBr₃ crystal.

When comparing a particular scintillation crystal having a compositiondescribed herein to a different scintillation crystal having a differentcomposition, a lower ER Ratio allows for more accurate detection ofenergy peaks. When comparing the scintillation crystals for particularenergies, the ER Ratio may be no greater than approximately 0.95 for anenergy of 8 keV. In another embodiment, the ER Ratio may be no greaterthan approximately 0.88, or more particularly, no greater than 0.80 foran energy of 8 keV. In a further embodiment, the ER Ratio may be in arange of approximately 0.79 to approximately 0.95 or more particularly,in a range of approximately 0.79 to approximately 0.86 for an energy of8 keV. At an energy of 13 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.88, or more particularly, no greater than0.80 for an energy of 13 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.78 to approximately 0.95 or moreparticularly, in a range of approximately 0.79 to approximately 0.88 foran energy of 13 keV.

At an energy of 17 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.90, or more particularly, no greater than0.80 for an energy of 17 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.76 to approximately 0.95 or moreparticularly, in a range of approximately 0.78 to approximately 0.90 foran energy of 17 keV. At an energy of 22 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.87 for an energy of 22 keV. In a further embodiment, the ER Ratiomay be in a range of approximately 0.84 to approximately 0.95 or moreparticularly, in a range of approximately 0.85 to approximately 0.90 foran energy of 22 keV.

At an energy of 26 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.86, or more particularly, no greater than0.80 for an energy of 26 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.75 to approximately 0.95 or moreparticularly, in a range of approximately 0.77 to approximately 0.90 foran energy of 26 keV. At an energy of 32 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.80 for an energy of 32 keV. In a further embodiment, the ER Ratiomay be in a range of approximately 0.75 to approximately 0.95 or moreparticularly, in a range of approximately 0.76 to approximately 0.90 foran energy of 32 keV.

At an energy of 44 keV, the ER Ratio may be no greater thanapproximately 0.97. In another embodiment, the ER Ratio may be nogreater than approximately 0.88, or more particularly, no greater than0.80 for an energy of 44 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.70 to approximately 0.97 or moreparticularly, in a range of approximately 0.73 to approximately 0.85 foran energy of 44 keV. At an energy of 60 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.80 for an energy of 60 keV. In a further embodiment, the ER Ratiomay be in a range of approximately 0.70 to approximately 0.95 or moreparticularly, in a range of approximately 0.76 to approximately 0.91 foran energy of 60 keV.

At an energy of 81 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.90, or more particularly, no greater than0.81 for an energy of 81 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.75 to approximately 0.95 or moreparticularly, in a range of approximately 0.79 to approximately 0.90 foran energy of 81 keV. At an energy of 276 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.85, or more particularly, no greaterthan 0.75 for an energy of 276 keV. In a further embodiment, the ERRatio may be in a range of approximately 0.70 to approximately 0.95 ormore particularly, in a range of approximately 0.73 to approximately0.85 for an energy of 276 keV.

At an energy of 303 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.88, or more particularly, no greater than0.83 for an energy of 303 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.80 to approximately 0.95 or moreparticularly, in a range of approximately 0.81 to approximately 0.90 foran energy of 303 keV. At an energy of 356 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.85 for an energy of 356 keV. In a further embodiment, the ERRatio may be in a range of approximately 0.80 to approximately 0.95 ormore particularly, in a range of approximately 0.81 to approximately0.86 for an energy of 356 keV.

At an energy of 384 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.90, or more particularly, no greater than0.85 for an energy of 384 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.80 to approximately 0.95 or moreparticularly, in a range of approximately 0.81 to approximately 0.88 foran energy of 384 keV. At an energy of 511 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.88, or more particularly, no greaterthan 0.83 for an energy of 511 keV. In a further embodiment, the ERRatio may be in a range of approximately 0.78 to approximately 0.95 ormore particularly, in a range of approximately 0.80 to approximately0.80 for an energy of 511 keV.

At an energy of 662 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.88, or more particularly, no greater than0.80 for an energy of 662 keV. In a further embodiment, the ER Ratio maybe in a range of approximately 0.74 to approximately 0.95 or moreparticularly, in a range of approximately 0.76 to approximately 0.85 foran energy of 662 keV. At an energy of 1173 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.80 for an energy of 1173 keV. In a further embodiment, the ERRatio may be in a range of approximately 0.70 to approximately 0.95 ormore particularly, in a range of approximately 0.74 to approximately0.90 for an energy of 1173 keV.

At an energy of 1274 keV, the ER Ratio may be no greater thanapproximately 0.95. In another embodiment, the ER Ratio may be nogreater than approximately 0.83, or more particularly, no greater than0.80 for an energy of 1274 keV. In a further embodiment, the ER Ratiomay be in a range of approximately 0.60 to approximately 0.95 or moreparticularly, in a range of approximately 0.64 to approximately 0.85 foran energy of 1274 keV. At an energy of 1332 keV, the ER Ratio may be nogreater than approximately 0.95. In another embodiment, the ER Ratio maybe no greater than approximately 0.90, or more particularly, no greaterthan 0.86 for an energy of 1332 keV. In a further embodiment, the ERRatio may be in a range of approximately 0.60 to approximately 0.95 ormore particularly, in a range of approximately 0.67 to approximately0.90 for an energy of 1332 keV.

For a Group 2 element, the improvement in ER Ratio can occur at allenergies. For a Group 1 element, the improvement in ER Ratio, can bemore readily seen at higher energies. In particular, for a scintillatorcrystal doped with a Group 1 element, the ER Ratio may become moresignificant at energies at 60 keV and higher, as compared to energieslower than 60 keV. Further, the improvement with ER Ratio with Group 1elements can be lower than the ER Ratio with a Group 2 element atenergies of 356 keV and higher. In particular, the ER Ratio with a Group1 element can be lower than 0.70. The actual ER Ratios may depend on theconcentration of the Group 1 element within the crystal. For example, atenergies between 44 keV and 60 keV, a scintillation crystal formed froma melt that includes 0.5 wt % NaBr can have ER Ratio less than 1, whilea a scintillation crystal formed from a melt that includes 2 wt % NaBrcan have ER Ratio greater than 1 at the same energies. After readingthis specification, skilled artisans will be able to determine dopantsand concentrations to provide an ER Ratio that meets the needs ordesires for a particular application.

Non-proportionality (nPR) refers to much a scintillation crystaldeviates perfect proportionality between gamma ray energy captured andlight output. A scintillation crystal having perfect proportionalitywould always create the same number of photons per unit energy absorbed,regardless of the energy of the gamma ray. Thus, its departure fromperfect proportionality is zero. For the purposes of this specification,nPR for each scintillation crystal is normalized at 662 keV. When nPR is100%, the photoelectrons at a particular energy, referred to as Z keVwill be:Ph_(Z keV,100% nPR)=Ph_(662 keV)*(Z keV/662 keV),

wherein Ph_(Z keV, 100% nPR) is the number of photoelectrons predictedto be sensed by a photosensor at an energy of Z keV when nPR is 100%,and

Ph_(662 keV) is the number of photoelectrons sensed by the photosensorat 662 keV.

Thus, nPR is:nPR=(Ph_(Z keV,measured)/Ph_(Z keV,100% nPR))*100%,

wherein Ph_(Z keV, measured) is the number of photoelectrons sensed bythe photosensor at an energy of Z keV.

The value of nPR is the same or improved at energies in a range of 10keV to 2000 keV when a Group 1 element or a Group 2 element is added asa co-dopant or a dopant in the melt when forming the crystal. The valueof nPR for rare earth halides when doped with a Group 2 element is moresignificant at lower energies than it is for higher energies. If thescintillation crystal generates less scintillating light for lowerenergy gamma rays, the scintillation crystal has poor proportionality.Thus, the response of the scintillation crystal to gamma rays at lowerenergies, such no greater than 60 keV, can be more significant toproportionality than the response at higher gamma ray energies, such asgreater than 60 keV. At energies lower than 30 keV, the improvement innPR can be even more significant as compared to 30 keV to 60 keV.

Proportionality can be determined with measuring the scintillationresponse at many different X-ray or gamma ray energies. A particularuseful method uses a tunable monochromatic synchrotron X-ray beam, suchas provided by the X1 beam line of Hamburger Synhrotronstrahlungslaborat Deutsches Elektronen-Synchrotron, Hamburg, Germany. Details for anexperimental setup can be found in “Nonproportional Response of LaBr:Ceand LaCl:Ce Scintillators to Synchrotron X-ray Irradiation,” by I. V.Khodyuk and P. Dorenbos, J. Phys. Condens. Matter, vol. 22, p. 485402,2010, which is incorporated herein for its detail regarding theexperimental setup. X-ray excited luminescence spectra can be recordedusing an X-ray tube with a Cu anode operating at 60 kV and 25 mA. Theemission of the sample can be focused via a quartz window and a lens onthe entrance slit of a monochromator, such as an ARC Model VM-504monochromator (available from Acton Research Corporation of Acton,Mass., US) (blazed at 300 nm, 1200 grooves/mm), dispersed and recordedwith a photomultiplier tube, such as a Hamamatsu Model R943-02 PMT(available from Hamamatsu Photonics Deutschland GmbH of Herrsching amAmmersee, Del.). The spectra can be corrected for the monochromatortransmission and for the quantum efficiency of the PMT. X-ray excitedluminescence measurements may be performed between 80 and 600K using acryostat. The PMT can be located outside the cryostat and be at roomtemperature.

The deviation from perfect proportionality (nPR_(dev)) is nPR minus100%. The parameter nPR_(dev) provides an value to quantify how much nPRis away from 100% and an indicator for direction; minus (−) is below100%, and plus (+) is above 100%. For a set of nPR data points, anaveraged value, a largest positive value, a largest negative value, amaximum value, an absolute value of any of the foregoing, a derivativeof any of the foregoing, or any combination thereof can be obtained. Theaveraged value can be an average, a median, or a geometric mean, or maybe determined using an integration. In a particular embodiment, theaverage deviation of nPR from 100% can be determined using an integralin accordance with the equation below.

${nPR}_{{dev}\mspace{14mu}{average}} = \frac{\int_{E_{lower}}^{E_{upper}}{{\left( \left( {{{nPR}\left( E_{i} \right)} - {100\%}} \right) \right. \cdot \ {dE}_{i}}}}{E_{upper} - E_{lower}}$

where

nPR(Ei) is nPR at energy E_(i);

E_(upper) is the upper limit of the energy range; and

E_(lower) is the lower limit of the energy range.

In the equation above, the absolute value of the deviation is used, andthus, any deviation, whether − or +, is accounted for within theequation. In particular, a positive deviation is not offset by anegative deviation. Thus, the measure provides a good indicator of thedegree of deviation over a range of energies

For a radiation energy range from 11 keV to 30 keV, the rare earthhalide scintillator crystal can have an nPR_(dev average) of no greaterthan approximately 8.0%, or more particularly no greater thanapproximately 5.0%, or even more particularly no greater thanapproximately 3.0%. For the radiation energy range of 30 keV to 60 keV,the rare earth scintillation crystal can have an nPR_(dev average) of nogreater than approximately 3.6%, or more particularly no greater thanapproximately 3.3%, or even more particularly no greater thanapproximately 2.9%.

For a radiation energy range from 60 keV to 356 keV, the rare earthhalide scintillator crystal can have an nPR_(dev average) of no greaterthan approximately 2.4%, or more particularly no greater thanapproximately 1.7%, or even more particularly no greater thanapproximately 0.7%. For the radiation energy range of 356 keV to 1332keV, the rare earth scintillation crystal has an nPR_(dev average) of nogreater than approximately 0.5%, or more particularly no greater thanapproximately 0.20%, or even more particularly no greater thanapproximately 0.07%.

CeBr₃ scintillation crystals may have values that depart more stronglyfrom perfect proportionality, as compared to LaBr₃:Ce scintillationcrystal. For a radiation energy range from 13 keV to 30 keV, the CeBr₃scintillation crystal can have an nPR_(dev average) of no greater thanapproximately 14%, or more particularly no greater than approximately12%, or even more particularly no greater than approximately 9%. For theradiation energy range of 30 keV to 60 keV, the CeBr₃ scintillationcrystal can have an nPR_(dev average) of no greater than approximately8.0%, or more particularly no greater than approximately 6.0%, or evenmore particularly no greater than approximately 4.0%.

For a radiation energy range from 60 keV to 356 keV, the CeBr₃scintillation crystal can have an nPR_(dev average) of no greater thanapproximately 2.0%, or more particularly no greater than approximately1.3%, or even more particularly no greater than approximately 0.7%. Forthe radiation energy range of 60 keV to 150 keV, the CeBr₃ scintillationcrystal can have nPR_(dev) average of no greater than approximately0.20%, or more particularly no greater than approximately 0.15%, or evenmore particularly no greater than approximately 0.09%.

Many different aspects and embodiments are possible. Some of thoseaspects and embodiments are described herein. After reading thisspecification, skilled artisans will appreciate that those aspects andembodiments are only illustrative and do not limit the scope of thepresent invention. Embodiments may be in accordance with any one or moreof the items as listed below.

Item 1. A scintillation crystal comprising Ln_((1-y))RE_(y)X₃:Me,wherein:

Ln represents a rare earth element;

RE represents a different rare earth element;

y has a value in a range of 0 to 1;

X represents a halogen;

Me represents a Group 1 element, a Group 2 element, or any mixturethereof; and

the scintillation crystal is formed from a melt having a Meconcentration of at least approximately 0.02 wt. %.

Item 2. A radiation detection apparatus comprising:

a scintillation crystal including Ln_((1-y))RE_(y)X₃:Me, wherein Lnrepresents a rare earth element; RE represents a different rare earthelement; y has a value in a range of 0 to 1; X represents a halogen; Merepresents a Group 1 element, a Group 2 element, or any mixture thereof;and the scintillation crystal is formed from a melt having a Meconcentration of at least approximately 0.02 wt. %; and

a photosensor optically coupled to the scintillation crystal.

Item 3. A scintillation crystal comprising:

a rare earth halide, wherein:

for a radiation energy range of 11 keV to 30 keV, the scintillationcrystal has an nPR_(dev average) of no greater than approximately 8.0%;or

for a radiation energy range of 30 keV to 60 keV, the scintillationcrystal has the nPR_(dev average) of no greater than approximately 3.6%.

Item 4. A scintillation crystal comprising:

a rare earth halide, wherein:

an energy resolution ratio is an energy resolution of the scintillationcrystal divided by a different energy resolution of a differentscintillation crystal having a different composition, wherein the energyresolution ratio is no greater than approximately 0.95 for an energy of8 keV; no greater than approximately 0.95 for an energy of 13 keV; nogreater than approximately 0.95 for an energy of 17 keV; no greater thanapproximately 0.95 for an energy of 22 keV; no greater thanapproximately 0.95 for an energy of 26 keV; no greater thanapproximately 0.95 for an energy of 32 keV; or no greater thanapproximately 0.97 for an energy of 44 keV.

Item 5. The scintillation crystal of claim 3 or 4, wherein thescintillation crystal has a general formula of Ln_((1-y))RE_(y)X₃,wherein:

Ln represents a rare earth element;

RE represents a different rare earth element;

y has a value in a range of 0 to 1; and

X represents a halogen.

Item 6. The scintillation crystal or radiation detection apparatus ofItem 5, wherein the scintillation crystal further comprises Me, whereinMe represents Li, Na, a Group 2 element, or any mixture thereof; and thescintillation crystal is formed from a melt having a Me concentration ofat least approximately 0.02 wt. %.

Item 7. The scintillation crystal or radiation detection apparatus ofany one of Items 1, 2, and 6, wherein the melt has the Me concentrationof at least approximately 0.08 wt %, at least approximately 0.2 wt. %,or more particularly at least approximately 0.3 wt. %, or even moreparticularly at least approximately 0.4 wt. %; or no greater thanapproximately 1.0 wt. %, or more particularly no greater thanapproximately 0.9 wt. %, or even more particularly no greater than 0.7wt. %.

Item 8. The scintillation crystal or radiation detection apparatus ofany one of Items 1, 2, 6, and 7, wherein the melt has the Meconcentration in range of approximately 0.2 wt. % to approximately 0.9wt. %, or more particularly in a range of approximately 0.3 wt. % toapproximately 0.7 wt. %.

Item 9. The scintillation crystal or the radiation detection apparatusof any one of Items 1, 2, and 6 to 8, wherein Me is the Group 2 element.

Item 10. The scintillation crystal or the radiation detection apparatusof Item 9, wherein Me is Ca, Sr, Mg, Ba, or any mixture thereof.

Item 11. The scintillation crystal or the radiation detection apparatusof Item 9, wherein Me is Ca.

Item 12. The scintillation crystal or the radiation detection apparatusof any one of Items 1, 2, and 6 to 8, wherein Me is the Group 1 element.

Item 13. The scintillation crystal or the radiation detection apparatusof Item 11, wherein Me is Li, Na, Rb, Cs, or any mixture thereof.

Item 14. The scintillation crystal or the radiation detection apparatusof Item 11, wherein Me is Li.

Item 15. The scintillation crystal or the radiation detection apparatusof any one of Items 1, 2, and 6 to 8, wherein Me includes at least twodifferent Group 1 elements; at least two different Group 2 elements; orat least one Group 1 element and at least one Group 2 element.

Item 16. The scintillation crystal or radiation detection apparatus ofany one of the preceding Items, wherein Ln includes La, Gd, Lu, or anymixture thereof.

Item 17. The scintillation crystal or radiation detection apparatus ofany one of the preceding Items, wherein RE includes Ce, Eu, Pr, Tb, Nd,or any mixture thereof.

Item 18. The scintillation crystal or radiation detection apparatus ofany one of the preceding Items, wherein y is no greater thanapproximately 0.5, or more particularly no greater than approximately0.2, or even more particularly no greater than approximately 0.09; or atleast approximately 0.005, or more particularly at least approximately0.01, or even more particularly at least approximately 0.02.

Item 19. The scintillation crystal or radiation detection apparatus ofany one of the preceding Items, wherein y is in a range of approximately0.01 to approximately 0.09, or more particularly in a range of at leastapproximately 0.03 to approximately 0.07.

Item 20. The scintillation crystal or radiation detection apparatus ofany one of the preceding Items, wherein Ln is La, RE is Ce, and X is Br.

Item 21. The scintillation crystal or radiation detection apparatus ofany one of Items 1 to 17 and 20, wherein y is approximately 1.0 f.u.

Item 22. The scintillation crystal or the radiation detection apparatusof Item 21, wherein for a radiation energy range of 13 keV to 30 keV,the scintillation crystal has a PR_(dev average) of no greater thanapproximately 14%, or more particularly no greater than approximately12%, or even more particularly 9%.

Item 23. The scintillation crystal or the radiation detection apparatusof Item 21 or 22, wherein for a radiation energy range of 30 keV to 60keV, the scintillation crystal has a PR_(dev average) of no greater thanapproximately 8.0% or more particularly no greater than approximately6.0%, or even more particularly no greater than 4.0%.

Item 24. The scintillation crystal or the radiation detection apparatusof any one of Items 21 or 23, wherein for a radiation energy range of 60keV to 356 keV, scintillation crystal has a PR_(dev average) of nogreater than approximately 2.0% or more particularly no greater thanapproximately 1.3%, or even more particularly no greater than 0.7%.

Item 25. The scintillation crystal or the radiation detection apparatusof any one of Items 21 to 24, wherein for a radiation energy range of356 keV to 1372 keV, scintillation crystal has a PR_(dev average) of nogreater than approximately 0.20% or more particularly no greater thanapproximately 0.15%, or even more particularly no greater than 0.09%.

Item 26. The scintillation crystal or the radiation detection apparatusof any one of Items 1, 2, and 6 to 20, wherein for a radiation energyrange of 11 keV to 30 keV, the scintillation crystal has aPR_(dev average) of no greater than approximately 8.0%; or for aradiation energy range of 30 keV to 60 keV, the scintillation crystalhas the PR_(dev average) of no greater than approximately 3.6%.

Item 27. The scintillation crystal or the radiation detection apparatusof any one of Items 1 to 20, and 26, wherein for a radiation energyrange of 11 keV to 32 keV, scintillation crystal has a PR_(dev average)of no greater than approximately 8.0% or more particularly no greaterthan approximately 5.0% or even more particularly no greater thanapproximately 3.0%.

Item 28. The scintillation crystal or the radiation detection apparatusof any one of Items 1 to 20, 26, and 27, wherein for a radiation energyrange of 30 keV to 60 keV, scintillation crystal has a PR_(dev average)of no greater than approximately 3.6% or more particularly no greaterthan approximately 3.3% or even more particularly no greater thanapproximately 2.9%.

Item 29. The scintillation crystal or the radiation detection apparatusof any one of Items 1 to 20, and 26 to 28, wherein for a radiationenergy range of 60 keV to 356 keV, scintillation crystal has aPR_(dev average) of no greater than approximately 2.4% or moreparticularly no greater than approximately 1.7% or even moreparticularly no greater than approximately 0.7%.

Item 30. The scintillation crystal or the radiation detection apparatusof any one of Items 1 to 20, and 26 to 29, wherein for a radiationenergy range of 356 keV to 1332 keV, scintillation crystal has aPR_(dev average) of no greater than approximately 0.50% or moreparticularly no greater than approximately 0.20% or even moreparticularly no greater than approximately 0.07%.

Item 31. The scintillation crystal or radiation detection apparatus ofany one of Items 3 and 22 to 30, wherein the averaged value fordeviation of nPR from 100% (nPR_(dev average)) is determined by:

${{nPR}_{{dev}\mspace{14mu}{average}} = \frac{\int_{E_{lower}}^{E_{upper}}{{\left( \left( {{{nPR}\left( E_{i} \right)} - {100\%}} \right) \right. \cdot \ {dE}_{i}}}}{E_{upper} - E_{lower}}},$where

nPR(Ei) is nPR at energy E_(i);

E_(upper) is the upper limit of the energy range; and

E_(lower) is the lower limit of the energy range.

Item 32. The scintillation crystal or the radiation detection apparatusof any one of the preceding Items, wherein an energy resolution ratio isan energy resolution of the scintillation crystal divided by a differentenergy resolution of a different scintillation crystal of a differentcomposition, wherein the energy resolution ratio is no greater thanapproximately 0.95 for an energy of 8 keV; no greater than approximately0.95 for an energy of 13 keV; no greater than approximately 0.95 for anenergy of 17 keV; no greater than approximately 0.95 for an energy of 22keV; no greater than approximately 0.95 for an energy of 26 keV; nogreater than approximately 0.95 for an energy of 32 keV; no greater thanapproximately 0.97 for an energy of 44 keV; no greater thanapproximately 0.95 for an energy of 60 keV; no greater thanapproximately 0.95 for an energy of 81 keV; no greater thanapproximately 0.95 for an energy of 276 keV; no greater thanapproximately 0.95 for an energy of 303 keV; no greater thanapproximately 0.95 for an energy of 356 keV; no greater thanapproximately 0.95 for an energy of 384 keV; no greater thanapproximately 0.95 for an energy of 511 keV; no greater thanapproximately 0.95 for an energy of 662 keV; no greater thanapproximately 0.95 for an energy of 1173 keV; no greater thanapproximately 0.95 for an energy of 1274 keV; no greater thanapproximately 0.95 for an energy of 1332 keV; or any combinationthereof.

Item 33. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32, wherein the energy resolution ratio is nogreater than approximately 0.95 for the energy of 8 keV, or moreparticularly no greater than approximately 0.88 for the energy of 8 keV,or still more particularly no greater than approximately 0.80 for theenergy of 8 keV.

Item 34. The scintillation crystal or the radiation detection apparatusof any one of Items 4, 32, and 33, wherein the energy resolution ratiois in a range approximately 0.79 to approximately 0.95 or moreparticularly in a range of approximately 0.79 to approximately 0.86 forthe energy of 8 keV.

Item 35. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 34, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 13 keV, or moreparticularly no greater than approximately 0.88 for the energy of 13keV, or still more particularly no greater than approximately 0.80 forthe energy of 13 keV.

Item 36. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 35, wherein the energy resolution ratiois in a range approximately 0.78 to approximately 0.95 or moreparticularly in a range of approximately 0.79 to approximately 0.88 forthe energy of 13 keV.

Item 37. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 36, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 17 keV, or moreparticularly no greater than approximately 0.90 for the energy of 17keV, or still more particularly no greater than approximately 0.80 forthe energy of 17 keV.

Item 38. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 37, wherein the energy resolution ratiois in a range approximately 0.76 to approximately 0.95 or moreparticularly in a range of approximately 0.78 to approximately 0.90 forthe energy of 17 keV.

Item 39. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 38, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 22 keV, or moreparticularly no greater than approximately 0.90 for the energy of 22keV, or still more particularly no greater than approximately 0.87 forthe energy of 22 keV.

Item 40. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 39, wherein the energy resolution ratiois in a range approximately 0.84 to approximately 0.95 or moreparticularly in a range of approximately 0.85 to approximately 0.90 forthe energy of 22 keV.

Item 41. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 40, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 26 keV, or moreparticularly no greater than approximately 0.86 for the energy of 26keV, or still more particularly no greater than approximately 0.80 forthe energy of 26 keV.

Item 42. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 41, wherein the energy resolution ratiois in a range approximately 0.75 to approximately 0.95 or moreparticularly in a range of approximately 0.77 to approximately 0.90 forthe energy of 26 keV.

Item 43. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 42, wherein an energy resolution ratiois no greater than approximately 0.95 for the energy of 32 keV, or moreparticularly no greater than approximately 0.90 for the energy of 32keV, or still more particularly no greater than approximately 0.80 forthe energy of 32 keV.

Item 44. The scintillation crystal or the radiation detection apparatusof anyone of Items 4 and 32 to 43, wherein the energy resolution ratiois in a range of approximately 0.75 to approximately 0.95 or moreparticularly in a range of approximately 0.76 to approximately 0.90 forthe energy of 32 keV.

Item 45. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 44, wherein the energy resolution ratiois no greater than approximately 0.97 for the energy of 44 keV, or moreparticularly no greater than approximately 0.88 for the energy of 44keV, or still more particularly no greater than approximately 0.80 forthe energy of 44 keV.

Item 46. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 45, wherein the energy resolution ratiois in a range approximately 0.70 to approximately 0.97 or moreparticularly in a range of approximately 0.73 to approximately 0.85 forthe energy of 44 keV.

Item 47. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 46, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 60 keV, or moreparticularly no greater than approximately 0.90 for the energy of 60keV, or still more particularly no greater than approximately 0.80 forthe energy of 60 keV.

Item 48. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 47, wherein the energy resolution ratiois in a range approximately 0.70 to approximately 0.95 or moreparticularly in a range of approximately 0.76 to approximately 0.91 forthe energy of 60 keV.

Item 49. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 48, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 81 keV, or moreparticularly no greater than approximately 0.90 for the energy of 81keV, or still more particularly no greater than approximately 0.81 forthe energy of 81 keV.

Item 50. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 49, wherein the energy resolution ratiois in a range approximately 0.75 to approximately 0.95 or moreparticularly in a range of approximately 0.79 to approximately 0.90 forthe energy of 81 keV.

Item 51. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 50, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 276 keV, or moreparticularly no greater than approximately 0.85 for the energy of 276keV, or still more particularly no greater than approximately 0.75 forthe energy of 276 keV.

Item 52. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 51, wherein the energy resolution ratiois in a range approximately 0.70 to approximately 0.95 or moreparticularly in a range of approximately 0.73 to approximately 0.85 forthe energy of 276 keV.

Item 53. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 52, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 303 keV, or moreparticularly no greater than approximately 0.88 for the energy of 303keV, or still more particularly no greater than approximately 0.83 forthe energy of 303 keV.

Item 54. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 53, wherein the energy resolution ratiois in a range approximately 0.80 to approximately 0.95 or moreparticularly in a range of approximately 0.81 to approximately 0.90 forthe energy of 303 keV.

Item 55. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 54, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 356 keV, or moreparticularly no greater than approximately 0.90 for the energy of 356keV, or still more particularly no greater than approximately 0.85 forthe energy of 356 keV.

Item 56. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 55, wherein the energy resolution ratiois in a range approximately 0.80 to approximately 0.95 or moreparticularly in a range of approximately 0.81 to approximately 0.86 forthe energy of 356 keV.

Item 57. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 56, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 384 keV, or moreparticularly no greater than approximately 0.90 for the energy of 384keV, or still more particularly no greater than approximately 0.85 forthe energy of 384 keV.

Item 58. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 57, wherein the energy resolution ratiois in a range approximately 0.80 to approximately 0.95 or moreparticularly in a range of approximately 0.81 to approximately 0.88 forthe energy of 384 keV.

Item 59. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 58, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 511 keV, or moreparticularly no greater than approximately 0.88 for the energy of 511keV, or still more particularly no greater than approximately 0.83 forthe energy of 511 keV.

Item 60. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 59, wherein the energy resolution ratiois in a range approximately 0.78 to approximately 0.95 or moreparticularly in a range of approximately 0.80 to approximately 0.88 forthe energy of 511 keV.

Item 61. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 60, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 662 keV, or moreparticularly no greater than approximately 0.88 for the energy of 662keV, or still more particularly no greater than approximately 0.80 forthe energy of 662 keV.

Item 62. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 61, wherein the energy resolution ratiois in a range approximately 0.74 to approximately 0.95 or moreparticularly in a range of approximately 0.76 to approximately 0.85 forthe energy of 662 keV.

Item 63. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 62, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 1173 keV, ormore particularly no greater than approximately 0.90 for the energy of1173 keV, or still more particularly no greater than approximately 0.80for the energy of 1173 keV.

Item 64. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 63, wherein the energy resolution ratiois in a range approximately 0.70 to approximately 0.90 or moreparticularly in a range of approximately 0.74 to approximately 0.90 forthe energy of 1173 keV.

Item 65. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 64, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 1274 keV, ormore particularly no greater than approximately 0.83 for the energy of1274 keV, or still more particularly no greater than approximately 0.80for the energy of 1274 keV.

Item 66. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 65, wherein the energy resolution ratiois in a range approximately 0.60 to approximately 0.95 or moreparticularly in a range of approximately 0.64 to approximately 0.85 forthe energy of 1274 keV.

Item 67. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 66, wherein the energy resolution ratiois no greater than approximately 0.95 for the energy of 1332 keV, ormore particularly no greater than approximately 0.90 for the energy of1332 keV, or still more particularly no greater than approximately 0.86for the energy of 1332 keV.

Item 68. The scintillation crystal or the radiation detection apparatusof any one of Items 4 and 32 to 67, wherein the energy resolution ratiois in a range approximately 0.60 to approximately 0.95 or moreparticularly in a range of approximately 0.67 to approximately 0.90 forthe energy of 1332 keV.

Item 69. The radiation detection apparatus of any one of Items 2 and 6to 68, wherein the radiation detection apparatus is a medical imagingsystem or a well logging apparatus.

EXAMPLES

The concepts described herein will be further described in the Examples,which do not limit the scope of the invention described in the claims.The Examples demonstrate performance of scintillation crystals ofdifferent compositions. Numerical values as disclosed in this Examplessection may be averaged from a plurality of readings, approximated, orrounded off for convenience.

Scintillator crystals were formed from an open crucible using differentcombinations of LaBr₃, CeBr₃, NaBr, SrBr₂, and BaBr₂. For the co-dopantsand dopants, the values in Table 1 reflect the amounts of the co-dopantsand dopants added to the melt.

TABLE 1 Crystal Compositions and Sample Sizes Sample Size CaBr₂ SrBr₂BaBr₂ NaBr (approx., Sample # Description (wt. %) (wt. %) (wt. %) (wt.%) cm₃) 1 Undoped — — — — 0.05 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 0.5 — —— 0.02 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped — 0.5 — — 0.1La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped — — 0.5 — 0.03 La_(0.95)Ce_(0.05)Br₃ 50.5% Na-doped — — — 0.5 0.1 La_(0.95)Ce_(0.05)Br₃ 6 2% Na-doped — — —2   0.01 La_(0.965)Ce_(0.035)Br₃ 7 Undoped CeBr₃ — — — — 0.05 8 Ca-dopedCeBr₃  .5 — — — 0.05 9 Sr-doped CeBr₃ —  .5 — — 0.05 10 Na-doped CeBr₃ —— — 0.5 0.05

Additional scintillation crystals were formed based on theLa_(0.95)Ce_(0.05)Br₃ formula and used 20 wt. % Na and 20 wt. % Na/20wt. % Sr in the melt. For these crystals and the crystals in Table 1,the crystal having the La_(0.95)Ce_(0.05)Br₃ formula with 20 wt. % Na/20wt. % Sr in the melt had cracks. The other crystals were transparent anddid not have cracks. Samples were obtained from the crystals and hadapproximate sizes as listed in Table 1.

The scintillation crystals were analyzed for energy resolution. Gammaray excited pulse-height spectra at room temperature were recorded witha Hamamatsu Model R1791 PMT connected to a Cremat Model CR-112pre-amplifier and an ORTEC Model 672 spectroscopic amplifier with 10 μsshaping time. The voltage of the PMT was set to 400 V to avoidsaturation due to intensive signals in short time interval. The barecrystals were mounted on the window of the PMT and covered with severalTeflon layers; all pulse-height measurements were performed inside anM-Braun UNILAB dry box with a moisture content less than 1 part permillion. The yield expressed in photoelectrons per MeV of absorbed gammaray energy (phe/MeV) was determined without an optical coupling betweenthe scintillator and the PMT-window. The yield was obtained from theratio between the peak position of the 662-keV photopeak and theposition of the mean value of the so-called single photoelectron peak inpulse-height spectra. Single photoelectron spectra were recorded with aHamamatsu Model R1791 PMT connected to a Cremat Model CR-110pre-amplifier. The absolute light yield expressed in photons per MeV(ph/MeV) was determined by correcting for the quantum efficiency andreflectivity of the PMT.

The energy resolution (“ER”) is obtained from the data collected usingthe samples and equipment as previously described. Tables 2 and 3include the energy resolution data for Samples 1 to 10.

TABLE 2 Energy Resolution Data 8 13 17 22 26 32 44 60 81 Sample #Description keV keV keV keV keV keV keV keV keV 1 Undoped 40.8 30.9 23.920.1 16.7 15.9 14.3 11.3 9.35 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 32.3 24.418.7 17.2 — 12.1 10.5 8.52 7.38 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 34.926.5 21.3 18.0 14.9 14.4 12.2 9.08 7.62 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped33.4 31.6 19.7 16.9 — 15.3 13.9 10.3 8.70 La_(0.95)Ce_(0.05)Br₃ 5 0.5%Na-doped 41.7 29.6 23.8 19.8 14.9 15.1 13.9 10.1 8.38La_(0.95)Ce_(0.05)Br₃ 6 2% Na-doped — — — — — 16.7 — 11.7 —La_(0.95)Ce_(0.05)Br₃ 7 Undoped 72.7 44.6 36.1 30.5 — 24.9 23.4 18.014.7 CeBr₃ 8 Ca-doped 53.4 36.0 29.7 24.8 — 19.2 17.8 13.6 11.3 CeBr₃ 9Sr-doped 55.5 34.1 28.6 23.7 — 18.3 16.9 12.8 10.7 CeBr₃ 10 Na-doped64.7 40.4 34.0 28.0 — 22.5 22.0 16.8 13.5 CeBr₃

TABLE 3 Energy Resolution Data 276 303 356 384 511 662 1173 1274 1332Sample # Description keV keV keV keV keV keV keV keV keV 1 Undoped 5.454.83 4.68 4.51 3.96 3.57 2.96 3.33 2.81 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped4.55 4.11 3.93 3.74 3.43 2.94 2.66 2.64 2.27 La_(0.95)Ce_(0.05)Br₃ 3Sr-doped 4.02 3.90 3.88 3.82 3.39 2.95 2.32 2.71 2.40La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped 5.37 4.88 4.97 4.62 4.37 3.8  3.24 4.132.52 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped 4.57 3.99 3.83 3.69 3.20 2.732.20 2.12 1.97 La_(0.95)Ce_(0.05)Br₃ 6 2% Na-doped — — — — — — — — —La_(0.95)Ce_(0.05)Br₃ 7 Undoped 7.50 6.80 6.98 5.60 5.71 4.93 4.51 4.673.09 CeBr₃ 8 Ca-doped 5.96 5.63 5.28 4.93 4.39 3.64 3.41 3.44 3.16 CeBr₃9 Sr-doped 6.00 5.05 4.81 4.40 4.03 3.45 3.00 2.73 2.60 CeBr₃ 10Na-doped 5.99 6.03 5.83 5.76 4.78 4.11 3.41 3.16 3.01 CeBr₃

FIGS. 2 and 3 include plots for the data for Samples 1 to 5. FIG. 2includes energy resolution the data for energies in a range of 8 keV to81 keV, and FIG. 3 includes the energy resolution data for energies in arange of 276 keV to 662 keV. FIGS. 4 and 5 include plots for the datafor Samples 7 to 10. FIG. 4 includes energy resolution the data forenergies in a range of 8 keV to 81 keV, and FIG. 5 includes the energyresolution data for energies in a range of 276 keV to 662 keV.

The energy resolution ratio (“ER Ratio) is the ratio of the energyresolution of a particular sample divided by the energy resolution ofanother sample. By using the ER Ratio, the comparison between twodifferent scintillation crystals should have less dependence on theenergy, as opposed to using only the energy resolution. Tables 4 and 5include the ER Ratio data. Samples 2 to 6 are compared to Sample 1, andSamples 8 to 10 are compared to Sample 7. For example, the ER Ratio forSample 2 (in Tables 4 and 5) is the ER for Sample 2 (in Tables 2 and 3)divided by the ER for Sample 1 (in Tables 2 and 3). “N/A” indicates thatthe ER Ratio is not applicable for the particular sample.

TABLE 4 ER Ratios 8 13 17 22 26 32 44 60 81 Sample # Description keV keVkeV keV keV keV keV keV keV 1 Undoped N/A N/A N/A N/A N/A N/A N/A N/AN/A La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 0.791 0.791 0.781 0.848 — 0.7620.730 0.757 0.789 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 0.857 0.860 0.8910.897 0.889 0.889 0.850 0.806 0.806 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped0.820 1.02  0.823 0.843 — 0.962 0.971 0.910 0.930 La_(0.95)Ce_(0.05)Br₃5 0.5% Na-doped 1.02  0.960 0.996 0.989 0.889 0.949 0.966 0.898 0.896La_(0.95)Ce_(0.05)Br₃ 6 2% Na-doped — — — — — 1.05  — 1.04  —La_(0.95)Ce_(0.05)Br₃ 7 Undoped N/A N/A N/A N/A N/A N/A N/A N/A N/ACeBr₃ 8 Ca-doped 0.732 0.807 0.822 0.812 0.771 0.771 0.769 0.754 0.765CeBr₃ 9 Sr-doped 0.762 0.763 0.791 0.778 0.733 0.733 0.722 0.708 0.725CeBr₃ 10 Na-doped 0.892 0.906 0.941 0.920 0.904 0.905 0.942 0.935 0.917CeBr₃

TABLE 5 ER Ratios 276 303 356 384 511 662 1173 1274 1332 Sample #Description keV keV keV keV keV keV keV keV keV 1 Undoped N/A N/A N/AN/A N/A N/A N/A N/A N/A La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 0.834 0.8510.840 0.829 0.866 0.824 0.899 0.793 0.808 La_(0.95)Ce_(0.05)Br₃ 3Sr-doped 0.738 0.807 0.829 0.847 0.856 0.826 0.784 0.814 0.854La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped 0.985 1.01  1.06  1.02  1.10  1.06 1.09  1.24  0.897 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped 0.839 0.8260.818 0.818 0.808 0.765 0.743 0.647 0.676 La_(0.95)Ce_(0.05)Br₃ 6 2%Na-doped — — — — — — — — — La_(0.95)Ce_(0.05)Br₃ 7 Undoped N/A N/A N/AN/A N/A N/A N/A N/A N/A CeBr₃ 8 Ca-doped 0.795 0.828 0.756 0.880 0.7690.738 0.756 0.737 1.02  CeBr₃ 9 Sr-doped 0.800 0.743 0.689 0.786 0.7060.700 0.665 0.858 0.840 CeBr₃ 10 Na-doped 0.799 0.887 0.835 1.03  0.8370.829 0.756 0.677 0.974 CeBr₃

The data show some variation in ER Ratios for each of the dopants. Thevariation for Samples 2 and 3 (Ca-doped and Sr-doped) have ER Ratioswith relatively low standard deviation. Sample 2 has an average ER Ratioof 0.81 and a standard deviation of 0.04, and Sample 3 has an average ERRatio of 0.84 and a standard deviation of 0.04. Sample 4 (Ba-doped) hasa significantly higher ER Ratio average of 0.99 and a standard deviationof 0.11. Sample 5 (Na-doped) has an intermediate ER Ratio of 0.86 and astandard deviation 0.11. The data suggest that, starting at 60 keV, theER Ratio for Sample 5 decreases with increasing energy. At 511 keV,Sample 5 has an ER Ratio less than 0.8, and at 1274 keV, Sample 5 has anER Ratio less than 0.7. Unlike Sample 5, Samples 2 to 4 do not appear tohave any discernible trends regarding ER Ratio as energy increases ordecreases.

Data for proportionality was also gathered. Proportionality was studiedwith a set of set of radioactive sources ⁶⁰Co, ²²Na, ¹³⁷Cs, ¹³³Ba,²⁴¹Am, plus Amersham variable energy X-ray source, and at the X-1beamline at the Hamburger Synchrotronstrahlungslabor (HASYLAB)synchrotron radiation facility in Hamburg, Germany using theexperimental setup previously references. X-ray excited luminescencespectra were recorded using an X-ray tube with Cu anode operating at 60kV and 25 mA. The emission of the sample was focused via a quartz windowand a lens on the entrance slit of an ARC Model VM-504 monochromator(blazed at 300 nm, 1200 grooves/mm), dispersed and recorded with aHamamatsu Model R943-02 PMT. The spectra were corrected for themonochromator transmission and for the quantum efficiency of the PMT.X-ray excited luminescence measurements were performed between 80 K and600 K using a Janis Model VPF-800 Cryostat operated with a LakeShoreModel 331 Temperature Controller. The PMT was outside the cryostat andremained at room temperature.

As previously discussed, the departure from perfect proportionality ismore significant at lower gamma ray energies because higher energy gammarays can collide with the scintillator crystal and result in lowerenergy gamma rays. Tables 6 and 7 include nPR data collected for thescintillation crystals when exposed to gamma ray energies in a range ofapproximately 8 keV to approximately 1332 keV. Table 8 includes nPR datacollected for the LaBr₃:Ce scintillation crystals when exposed to gammaray energies in a range of approximately 11 keV to approximately 100keV. Table 9 includes nPR data collected for the CeBr₃ scintillationcrystals when exposed to gamma ray energies in a range of approximately13 keV to approximately 100 keV. Data collected at 662 keV was used fordetermining the nPR data in Table 6 to 9.

TABLE 6 nPR Data 8 13 17 22 26 32 44 60 81 Sample # Description keV keVkeV keV keV keV keV keV keV 1 Undoped 90.4 96.8 94.1 95.7 96.9 98.4 97.798.6 99.6 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 100 105   103 103 — 104 103104 102 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 98.0 102   100 101 100   102101 102 102 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped 96.5 — 99.3 101 101   101101 102 101 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped 88.8 96.4 94.2 96.197.0 98.3 97.0 99.4 99.8 La_(0.95)Ce_(0.05)Br₃ 7 Undoped 71.1 81.7 82.285.7 — 90.4 90.0 91.6 95.0 CeBr₃ 8 Ca-doped 84.5 93.2 92.1 94.9 — 96.896.0 98.4 98.8 CeBr₃ 9 Sr-doped 84.7 93.5 92.9 95.4 — 97.5 96.1 97.799.2 CeBr₃ 10 Na-doped 74.0 83.3 83.8 87.3 — 91.8 91.4 92.8 96.4 CeBr₃

TABLE 7 nPR Data 276 303 356 384 511 662 1173 1274 1332 Sample #Description keV keV keV keV keV keV keV keV keV 1 Undoped 100 100 100100 101 100 100 100 100 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 101 101 101 101101 100 100 100 100 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 101 101 100 100 101100 100 100 100 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped 101 101 100 101 101 100100 100 100 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped 100 101 101 100 101100 100 100 100 La_(0.95)Ce_(0.05)Br₃ 7 Undoped 99.3 100 100 100 100 100100 100 101 CeBr₃ 8 Ca-doped 100 100 100 100 100 100 100 100 100 CeBr₃ 9Sr-doped 100 100 100 100 100 100 100 100 100 CeBr₃ 10 Na-doped 100 101101 100 101 100 100 100 100 CeBr₃

TABLE 8 nPRs Data Energy Undoped Sr-doped Ca-doped (keV)La_(0.95)Ce_(0.05)Br₃ La_(0.95)Ce_(0.05)Br₃ La_(0.95)Ce_(0.05)Br₃ 1186.7 100 97.3 12 87.9 101 99.7 15 88.2 100 100 20 90.9 102 103 25 93.4103 105 30 95.1 103 105 35 96.3 103 104 38 96.7 103 104 48 95.8 102 10350 96.2 102 103 55 96.8 102 103 60 97.2 102 103 65 97.4 102 103 70 97.9102 103 75 98.0 102 103 80 98.3 102 103 85 98.5 102 102 90 98.5 102 10295 98.6 102 102 100 98.8 102 102

TABLE 9 nPRs Energy Undoped Sr-doped (keV) CeBr₃ CeBr₃ 13 80.6 90.1 1578.7 88.1 20 84.3 92.0 25 88.0 94.4 30 90.6 95.9 35 92.4 96.6 40 93.597.3 45 91.0 95.6 50 92.1 96.3 55 93.0 96.9 60 93.6 97.3 65 95.4 97.4 7094.9 97.6 75 95.3 97.6 80 95.9 97.8 85 96.2 97.9 90 96.4 97.9 95 96.698.0 100 96.9 98.1

FIGS. 6 and 7 include plots that include the data for Samples 1 to 5,which are the La_(0.95)Ce_(0.5)Br₃ samples. FIG. 6 includes energyresolution the data for energies in a range of 8 keV to 1332 keV. Theplot shows that the Samples 2 to 4 (Ca-doped, Sr-doped, and Ba-doped)have nPRs values that are much closer to 100% for lower energies, ascompared to Sample 1 (undoped). Sample 5 (Na-doped) does not appear tohave any significant improvement for nPR as compared to Sample 1. FIG. 7includes the nPR data for Samples 1 to 3 for energies in a range of 9keV to 100 keV. The difference between Sample 1 and each of Samples 2and 3 is apparent in FIG. 7. The difference between Sample 1 and each ofSamples 2 and 3 is more evident at energies of 32 keV and lower. Fromthe data, Sample 3 appears to have proportionality that is the closestto perfect proportionality over the energy ranges tested, as compared tothe other Samples. Sample 2 has slightly less uniform proportionalitythan Sample 3 and has significantly better proportionality as comparedto Samples 1 and 5.

FIGS. 8 and 9 include plots that include the data for Samples 7 to 10,which are the CeBr₃ samples. FIG. 8 includes energy resolution the datafor energies in a range of 8 keV to 1332 keV. The plot shows that theSamples 8 and 9 (Ca-doped and Sr-doped) have nPRs values that are muchcloser to 100% for lower energies, as compared to Sample 7 (undoped).Samples 8 and 9 have proportionalities that are close to each other overthe range of energies tested. Sample 10 (Na-doped) does not appear tohave any significant improvement for nPR as compared to Sample 7. FIG. 9includes the nPR data for Samples 7 and 9 for energies in a range of 10keV to 100 keV. The difference between Sample 7 and Sample 9 is apparentin FIG. 9. The difference between Sample 7 and Sample 9 is more evidentat energies of 32 keV and lower.

The amount of deviation from 100% and the direction of the deviation canbe obtained by subtracting 100% from the nPR values, which is nPR_(dev)that is also in units of %. The equation is provided below.inPR _(dev)=nPR−100%.

Tables 10 to 13 include the nPR_(dev) data that is derived from the nPRdata in Tables 6 to 9.

TABLE 10 nPR_(dev) Data 8 13 17 22 26 32 44 60 81 Sample # DescriptionkeV keV keV keV keV keV keV keV keV 1 Undoped −9.6 −3.2 −5.9 −4.3 −3.1−1.6 −2.3 −1.4 −0.4 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 0.3 4.6 2.5 3.1 —3.7 3.0 3.5 2.2 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped −2.0 1.5 −0.1 0.5 0.31.8 1.2 2.3 1.9 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped −3.5 — −0.3 0.7 1.1 1.30.7 1.5 1.2 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped −11.2 −3.6 −5.8 −3.9−3.0 −1.7 −2.3 −0.6 −0.2 La_(0.95)Ce_(0.05)Br₃ 7 Undoped −28.9 −18.3−17.8 −14.3 — −9.6 −10.0 −8.4 −5.0 CeBr₃ 8 Ca-doped −26.0 −6.8 −7.9 −5.2— −3.2 −4.0 −1.6 −1.3 CeBr₃ 9 Sr-doped −15.3 −6.5 −7.1 −4.6 — −2.5 −3.9−2.3 −0.8 CeBr₃ 10 Na-doped −15.5 −16.7 −16.2 −12.7 — −8.2 −8.6 −7.2−3.6 CeBr₃

TABLE 11 nPR_(dev) Data 276 303 356 384 511 662 1173 1274 1332 Sample #Description keV keV keV keV keV keV keV keV keV 1 Undoped 0.1 0.4 0.30.3 0.8 0.0 0.0 0.0 0.1 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 0.7 0.7 0.6 0.50.9 0.0 0.1 0.2 0.1 La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 0.6 0.6 0.4 0.2 0.50.0 0.1 −0.1 0.0 La_(0.95)Ce_(0.05)Br₃ 4 Ba-doped 0.7 0.6 0.4 0.5 0.50.0 0.1 0.2 0.3 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na-doped 0.3 0.5 0.5 0.20.6 0.0 −0.2 −0.4 −0.5 La_(0.95)Ce_(0.05)Br₃ 7 Undoped −0.7 −0.4 −0.30.1 0.1 0.0 0.0 0.4 0.6 CeBr₃ 8 Ca-doped −0.2 0.2 0.1 0.2 0.5 0.0 0.10.2 0.3 CeBr₃ 9 Sr-doped −0.1 0.1 0.1 0.0 0.4 0.0 0.0 0.0 0.0 CeBr₃ 10Na-doped 0.0 0.5 0.6 0.4 0.5 0.0 0.2 0.3 0.2 CeBr₃

TABLE 12 nPR _(dev) Data Energy Undoped Sr-doped Ca-doped (keV)La_(0.95)Ce_(0.05)Br₃ La_(0.95)Ce_(0.05)Br₃ La_(0.95)Ce_(0.05)Br₃ 11−13.3 0.38 −2.62 12 −12.1 0.02 0.32 15 −11.8 0.12 0.16 20 −9.03 1.623.45 25 −6.60 1.88 4.55 30 −4.85 2.58 4.63 35 −3.68 2.79 4.11 38 −3.272.62 3.74 48 −4.20 2.24 3.19 50 −3.80 2.26 3.22 55 −3.24 2.36 3.16 60−2.82 2.30 3.00 65 −2.55 2.23 2.89 70 −2.08 2.12 2.87 75 −2.00 1.99 2.5880 −1.67 1.96 2.59 85 −1.52 1.94 2.49 90 −1.45 1.78 2.30 95 −1.35 1.692.18 100 −1.21 1.70 2.10

TABLE 13 nPR _(dev) Data Energy Undoped Sr-doped (keV) CeBr₃ CeBr₃ 13−19.4 −9.88 15 −21.3 −11.9 20 −15.7 −9.02 25 −12.0 −5.59 30 −9.42 −4.1235 −7.60 −3.38 40 −6.46 −2.66 45 −9.00 −4.41 50 −7.85 −3.72 55 −6.95−3.09 60 −6.37 −2.70 65 −5.47 −2.58 70 −5.06 −2.42 75 −4.65 −2.37 80−4.13 −2.25 85 −3.80 −2.10 90 −3.54 −2.05 95 −3.36 −2.00 100 −3.06 −1.89

FIGS. 8 and 9 include plots for the data for Samples 7 to 10, which arethe CeBr₃ samples. FIG. 8 includes energy resolution the data forenergies in a range of 8 keV to 1332 keV. The plot shows that theSamples 8 and 9 (Ca-doped and Sr-doped) have nPRs values that are muchcloser to 100% for lower energies, as compared to Sample 7 (undoped).Samples 8 and 9 have proportionalities that are close to each other overthe range of energies tested. Sample 10 (Na-doped) does not appear tohave any significant improvement for nPR, as compared to Sample 7. FIG.9 includes the nPR data for Samples 7 and 9 for energies in a range of10 keV to 100 keV. The difference between Sample 7 and Sample 9 isapparent in FIG. 9. The difference between Sample 7 and Sample 9 is moreevident at energies of 32 keV and lower.

Data for nPR_(dev) can be used to determine an nPR_(dev average) for aparticular range of energies. Table 14 includes nPR_(dev average)determined as previously described.

TABLE 14 nPR _(dev average) Data 11 or 13 Sample keV to 30 keV to 60 keVto 356 keV to # Description 30 keV 60 keV 356 keV 1332 keV 1 Undoped 8.93.7 0.26 0.15 La_(0.95)Ce_(0.05)Br₃ 2 Ca-doped 2.6 3.6 1.3 0.23La_(0.95)Ce_(0.05)Br₃ 3 Sr-doped 1.3 2.5 1.2 0.13 La_(0.95)Ce_(0.05)Br₃4 B a-doped — — 0.90 0.17 La_(0.95)Ce_(0.05)Br₃ 5 0.5% Na- — — 0.63 0.22doped La_(0.95)Ce_(0.05)Br₃ 7 Undoped 15.8 7.7 2.5 0.08 CeBr₃ 8 Ca-doped— — 0.63 015 CeBr₃ 9 Sr-doped 8.0 3.4 0.43 0.06 CeBr₃ 10 Na-doped — —1.7 0.20 CeBr₃

Data for nPR_(dev average) is good for distinguishing which samples aremore proportional over one or more ranges of energies. For theLa_(0.95)Ce_(0.05)Br₃ samples, Sample 3 (Sr-doped) has the bestperformance over all the energies, particularly at energies from 11 keVto 60 keV. Sample 2 has good proportionality at 11 to 30 keV. Atenergies in a range of 30 to 60 keV, Sample 2 has nearly the samemagnitude of deviation from proportionality as compared to Sample 1. Thedeviation for Samples 1 and 2 are in opposite directions (− for Sample 1and + for Sample 2). For energies in a range of 60 keV to 356 keV,Samples 2 to 4 have positive deviation from 100%, and Sample 1 hasdeviation from 100% that is closer to zero. For energies in a range of356 keV to 1332 keV, the Samples 1 to 5 have nPR_(dev average) valuesthat are less than 0.1% different from one another.

For the CeBr₃ samples, Sample 9 (Sr-doped) has the best performance overall the energies, particularly at energies from 11 keV to 60 keV.Although Sample 8 (Ca-doped) does not have as much data, therelationship between Samples 8 and 9 for nPR_(dev average) is expectedto be about the same as the relationship between Samples 2 and 3 fornPR_(dev average). For energies in a range of 60 keV to 356 keV, Samples8 and 9 have better proportionality compared to Sample 7 (undoped). Forenergies in a range of 356 keV to 1332 keV, the Samples 7 to 9 havenPR_(dev average) values that are less than 0.1% different from oneanother.

Data have been taken on the relative response of standard and co-dopedlanthanum bromide versus temperature. The samples include LaBr₃(Ce),LaBr₃(Ce,Sr) and LaBr₃(Ce,Ba). The cerium concentration in each samplewas 4.5 to 5%, meaning that 4.5 to 5% of the La atoms were replaced byCe. The Sr concentration was 180 parts per million by weight, and the Baconcentration was 160 parts per million by weight. Each crystal wasformed as a right circular cylinder with dimensions where the diameterwas approximately 2.5 cm and length was approximately 2.5 cm. The lightoutput was measured by locating the centroid of the 662 keV photopeakfrom a 10 micro-Ci ¹³⁷Cs gamma ray source. The source was placed at adistance of 10 mm from one end of the crystal. The other end was coupledto a photomultiplier tube (model: Photonis 20Y0) that was kept at aconstant 30° C.

FIG. 10 includes a plot showing the temperature response of standard,LaBr₃(Ce), LaBr₃(Ce,Sr) and LaBr₃(Ce,Ba). Specifically, the graph showshow the scintillation light output changes with temperature from −40° C.to 175° C. Each curve is normalized to 1.0 at 25° C. When co-doped withSr, the light output is more constant than standard over the range of−40° C. to 175° C., and is measurably brighter than standard at thehighest temperatures. This makes Sr co-doped lanthanum bromide desirablefor applications that involve extreme temperature excursions, such asoil well logging and space applications. When co-doped with Ba, thelight output increases over the range of room temperature (approximately22° C.) to about 70° C. This makes Ba co-doped lanthanum bromidedesirable for outdoor applications, for example for port-of-entrydetectors that can be used for vehicles and cargo.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed is not necessarily the order inwhich they are performed.

Certain features that are, for clarity, described herein in the contextof separate embodiments, may also be provided in combination in a singleembodiment. Conversely, various features that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges includes each and every value within that range.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

The specification and illustrations of the embodiments described hereinare intended to provide a general understanding of the structure of thevarious embodiments. The specification and illustrations are notintended to serve as an exhaustive and comprehensive description of allof the elements and features of apparatus and systems that use thestructures or methods described herein. Separate embodiments may also beprovided in combination in a single embodiment, and conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges includes each and everyvalue within that range. Many other embodiments may be apparent toskilled artisans only after reading this specification. Otherembodiments may be used and derived from the disclosure, such that astructural substitution, logical substitution, or another change may bemade without departing from the scope of the disclosure. Accordingly,the disclosure is to be regarded as illustrative rather thanrestrictive.

What is claimed is:
 1. A method, comprising: placing into a crucibleprecursors including: a rare earth halide precursor; and a Ca halideprecursor; melting the precursors to form a melt, wherein aconcentration of the Ca halide is at least
 0. 02wt. %; forming ascintillation crystal including Ln(_(1-y))RE_(y)X₃:Ca, wherein: Lnrepresents a rare earth element; RE represents a different rare earthelement; y has a value in a range of 0 to 1; and X represents a halogen;and optically coupling an optical interface to the scintillationcrystal.
 2. The method of claim 1, wherein RE is Ce.
 3. The method ofclaim 2, wherein Ln is La.
 4. The method of claim 3, wherein X is Br. 5.The method of claim 2, wherein y is 1.0 f.u.
 6. The method of claim 1,wherein the concentration of the Ca halide in the melt is no greaterthan 1.0 wt. %.
 7. The method of claim 1, wherein y is no greater than0.5 and at least
 0. 005.
 8. The method of claim 1, wherein y is in arange of 0.01 to 0.09.
 9. The method of claim 1, wherein for a radiationenergy range of 13 keV to 30 keV, the scintillation crystal has a PR_(dev average) of no greater than 14%, or for a radiation energy rangeof 30 keV to 60 keV, the scintillation crystal has a PR _(dev average)of no greater than 8.0%.
 10. The method of claim 1, wherein: for aradiation energy range of 11 keV to 30 keV, the scintillation crystalhas a PR _(dev average) of no greater than 8.0%; or for radiation energyrange of 30 keV to 60 keV, the scintillation crystal has the PR_(dev average) of no greater than 3.6%.
 11. The method of claim 1,wherein an energy resolution ratio is an energy resolution of thescintillation crystal divided by a different energy resolution of adifferent scintillation crystal of a different composition, wherein theenergy resolution ratio is: no greater than 0.95 for an energy of 8 keV;no greater than 0.95 for an energy of 13 keV; no greater than 0.95 foran energy of 17 keV; no greater than 0.95 for an energy of 22 keV; nogreater than 0.95 for an energy of 26 keV; no greater than 0.95 for anenergy of 32 keV; or no greater than 0.97 for an energy of 44 keV. 12.The method of claim 11, wherein the energy resolution ratio is nogreater than 0.95 for the energy of 8 keV.
 13. The method of claim 11,wherein the energy resolution ratio is no greater than 0.95 for theenergy of 13 keV.
 14. The method of claim 11, wherein the energyresolution ratio is no greater than 0.95 for the energy of 17 keV. 15.The method of claim 11, wherein the energy resolution ratio is nogreater than 0.95 for the energy of 22 keV.
 16. The method of claim 11,wherein the energy resolution ratio is no greater than 0.95 for theenergy of 26 keV.
 17. The method of claim 11, wherein an energyresolution ratio is no greater than 0.95 for the energy of 32 keV. 18.The method of claim 1, further comprising optically coupling aphotosensor to the optical interface.